Composition of matter



Patented Mar. 26, 1940,

UNITED STATES P TENroFFicE 2,194,643 COMPOSITION OF MATTER Melvin De Groote, University City, Mo., assignor,

by mesne assignments, to Petrolite Corporation, Ltd.,' a corporation of Delaware No Drawing. Application'Mar-eh 10, 1939,

I Serial N0. 261,091

Claims;

This application is a continuation in part of my pending application for'. patent Serial No. 211,036, filed May 31, 1938, which has subsequently resulted in U. S. Patent No. 2,166,431, dated 5 July 18,. 1939.

My present invention consists of a new com- I have found that saidnew compound is par One can obtain or manufacture chemical compounds whose compositionis indicated by the following formulas:

v "onaoooolnm onaooooinom'r The compounds above described may be summarized by the following formula: M

v oH.Rooo.o,Hl)..N

I )m" in which m represents the numeral 1, 2, or 3, m represents'the numeral 0, 1, or 2, and m" represents the numeral 0, 1, -or 2, with the proviso that l+ n 3" I However, the radieal QzH4 which appears in the above formula may represent any similar r radical, such as a CsHs radical, C4Ha radical, etc., and therefore, the above formula may be rewritten: a

1).. oaaoooanmm ndra (Cl. 260-404) where n represents a small w hole number preferably not over '10. Y

In the above formulas, T represents a nonhydroxy aliphatic hydrocarbon radical, such as a methyl, ethyl, propyl, amyl, or similar radical; 5 or T may represent a non-hydroxy alicyclic radical, .such as a cyclohexyl radical, or a non-hydroxy aralkyl radical, such as a benzyl radical; or. the acylated radical obtained by replacing abydrogen atom of the hydroxyl group of an alkylol 0 radical by the acyl radical of a monobasic carboxy acid, such as acetic acid; butyric acid, oleic acid, stearic acid, naphthenic acid, abi etic acid, or the like, all of which are charaterized by having less than 32 carbon atoms." The alkylol radi- 15 cal prior to acylation may be a" hydroxy alicyclic or a hydroxy aralkyl radicahprovided that the hydroxy radical is attached to the aliphatic residue of the aralkylradical. In the above formulas, OH.RCOOH represents a hydroxylated 20 fatty acid, such as ricinoleic acid, hydroxystearic acid, dihydroxystearic acid, diricinoleic acid, triricinoleic acid, polyricinoleic acid, etc.; and OHRCOO represents the oxy acyl radical derived from such acid, i. e., the ordinary acid radical. Blown oils (oxidized oils) are not included.

As to the amines above described which happen to be tertiary amines, it may be well to point out thatthese may be formed readily by a reaction involving an ester of the hydroxylated fatty acid and a correspondingamine. This may be illustrated in the following manner:

Reference is made to co-pending application for patent Serial No. 180,993, filed December 21, 1937, by Melvin De Groote, Bernhard Keiser, and Charles M. lair, Jr.- If ,triethanolamine, as employed in th above formulas, is replaced by ethyl 4 diethanola a e, or by diethyl ethanolamine, then one would readily 'obtain the other two types. of tertiary i amines illustrated. Reference is made to co-pending application for patent Serial P No. 206,904, filed May 9; 1938, by -'M elvin De 4 Groote, Bernhard K eiser,1 and CharlesM. Blair, Jr., which subsequently resulted in U. S. Patent No. 2,167,349, dated July 25, 1939.

In the remaining three types=of materials there is at least one amino hydrogen atom present. The manufacture of such type material may be illustrated by the following reactions:

' following:

OH.R.C00.cI 4cl+Nfig 0H.R.C00.0:H4NH8 20311.0oo.CiHc1+NH;- 0H.R.c00.0iH0iNH OH.R.COO.C:H4Cl+C H NH,-r0H.R.C00.0:Hi

i Y H Similar reactions to the one immediately preceding result in compounds, such as:

OH.R.COO.CHA OH.R.C0O.C:H4

NE NH Ct u a sC However, if maximum yields are not necessary, one need not resort to reactions of the kind previously described to produce amines having at least one amino hydrogen, but one may employ the following reactions:

Naturally, if ethyl ethanolamine or a similar amine were to replace ethanolamine (monoethanolamine), one would obtain the remaining tripropanolamine, dipropanol methylamine, cy-

clohexanol diethanolamine, dicyclohexanol ethanolamine, cyclohexyl diethanolamine, dicyclo- -hexyl ethanolamine, dicyclohexanol ethylamine ben'zyl diethanolamine, dibenzylethanolamine,

benzyl- -dipropanolamine, tripentanolamine, trihexanolamine, ethyl hexyl ethanolamine, octadecyl diethanolamine, polyethanolamine, etc.

It is also known that one may have amines of the type:

Gallic CIHAOH canon canon CiHlO C1HAOH CzH O CrH OH Such amines may serve as functional equivalents of the previously described amines.

All the amines of the kind above described and characterized .by the formula:

(OERCOQC-HIJ-N in which n represents a small whole number,

preferably less than 10, and m represents the numeral 1, 2, or 3, m represents the numeral 0, 1, or 2, and m" represents the numeral 0, 1, or 2, with the proviso that m+m'+km"=3, have four common characteristics. In the first place, these amines are not quaternary ammonium bases or salts thereof. The expression quaternary ammonium is properly and conventionally ap- 4 plied to compounds in which all four hydrogen atoms of the ammonium radical NH4 have been replaced by a-hydrocarbon radical or oxy.-hydr0- carbon radical, vas, for example, in trimethyl phenyl ammonium hydroxide.

, Secondly, an important characteristic which must be recognized is that these amine compounds are not amides. It is to be noted that an amide formation involves a product in which there is a direct linkage'between the carboxylic carbon atom and the nitrogen atom in the amine. This is not the case in the compounds employed as intermediate raw materials for production of the compounds used as demulsifying agents in the present process. 1

In the third place, it must be recognized that these compounds are derived only from basic amines. The word basic is employed to exclude amines having little or no basicity, such as the ordinary aromatic .amines, or any amine having at least one aryl radical directly joined to the amino nitrogen atom. For this reason, these amine products which are herein contemplated as demulsifying agents in the resolution I of petroleum emulsions, and which necessarily are characterized by freedom from any aryl groups as such, cannot be derived from aryl amines. They are derived solely from alkyl, alicyclic or aralkyl amines having at least one hydroxyl group present. It is true that in the aralkyl amines there is an aryl group present, but it is not directly attached to the nitrogen atom, as in the case of aryl amines, but, in fact, represents nothing more or less than a substituted alkylamine. For instance, I consider benzylamine as being the primary amine, phenmethyl amine. I

Finally, it must be recognized that these materials have not lost any basicity in the forms 'of the esterified amine and that they exhibit all the properties of a basic amine, that is, they combine with water to form a base presumably a substituted ammonium compound, but not quaternary ammonium compounds, insofar that there are always one, two or three unsubstituted'hydrogen atoms of the ammonium radical present.

They combine with various acids to form salts. For example, they may be combined with acetic tributed in part by the amine, and it is immaterial whether the amine may be considered as being in any one of the following forms:

- mediate raw materials, viz.:

'in which the charactershave their previous significance.

Attention is directed to the fact that wherethe substitutedalkyl radical OH.R.COO.C2H4 appears, a suitable non-aryl radical other than an aliphatic residue may serve as the functional equivalent; for instance, an alicyclic radical derived frorn a cyclohexyl radical or an aralkyl radical derived from a benzyl radicaL- In other words, in the hereto appended claims reference to the CnHZn radical, as such; or as an 'alkyl radicalor residue, is intended in the broad] sense to include the alicyclic radicals or residues, 'or the aralkyl radicals or residues which are the equivalent thereof. There is no intention to include an aromatic radical where there is a direct linkage between the aromatic nucleus and the amino hydrogen atom, for the reason that such products have little or no basicity and do not have the characteristic properties of the amines previously described.

In indicating the various hydroxylated terti amines of the non-aryl type which may .be employed to produce the amine herein described, it is desirable to indicate that amines of the type where a hydroxy acyl radical replaces a hydrogen atom of a hydroxyl radical of the hydroxy tertiary amine, are not included within the broad class of hydroxy tertiary amines, unless there is another hydroxyl radical attached to the usual alkyl radical. For instance, if diethyl amino ethanol is treated with lactic acid, so as to form lactyl ethanol diethylamine of the following formula:

then it is understood that such materials would not represent a hydroxy tertiary amine within the meaning or scope, as herein employed. If on the other hand, triethanolamine were treated with lactic acid, 'so as to give 'monoiactyl triethanolamine of the following composition:

OH O r oHutr c o-onn OHCaHa then such compound would be included, due to I the presence of one or more hydroxyl radicals attached to the alkyl radicals.

Similarly, in indicating the various hydroxylated-primary or secondary amines of the non-aryl type which may be employed to produce the amine herein described, it is desirable to indicate that amines of the type where a hydroxy acyl radical replaces the hydrogen atom of the hydroxyl radical of a hydroxy primary or secondary amine, are not included within the broad class of hydroxy tertiary amines, unless there is another hydroxyl radical attached to the usual alkyl radical. For instance, if ethanolamine is treated with lactic acid, so as to form the lactyl derivative of the following formula:

on' o cmcn.o o c|rhmm then it is understood that such materials would not represent a hydroxy primary amine within the meaning or scope, as herein employed. The same would be true if the corresponding product were derived from diethanolamine, provided that both hydroxy radicals had been esterifledwith lactic acid. 'If, on the other hand, diethanolamine were treated with lactic acid, so as to give monolactyl diethanolamine of the following 'the presence of the hydroxyl radicals attached to the alkyl radicals.

The manufacture of compounds from tertiary amines 'is relatively simple, because no precautions are necessary to prevent amidiflcation. The

selected fatty oil and the selected hydroxy ter-- tiary amine are mixed in suitable proportions and heated at some point above the boiling point of water, for instance, (3., and at a point below the decomposition point of the amine or the fatty oil, for instance, 0., for a. suitable period of time, such as two to eight hours.- Mild agitation is employed. A catalyst such as sodium oleate, sodium carbonate, caustic soda, etc., may 7 be present in amounts of about one-half of1% or less. It is noted that the fatty acids are employed in this instance in the form of an '9 ester, towit, the glyceride, although, as previously pointed out, other functional equivalents can be readily employed with equal facility. It

' is to be noted that the reactions above described do not take place to any appreciable extent if the fatty acid has been converted into the soap or salt. Such salts are not functional equivalents.

'When, however, one is employing a hydroxy primary or .a hydroxy secondaryamine, precautions must be taken so that one gets a substantial percentage of products derived by esteriflcation,

rather than amidiflcation. -Any suitable ester may be employed, but it is often most convenient primary or secondary amine are mixed in suitable proportions and heated at some point above the boiling point of water, for instance, 110 C., and

below the decomposition point of the amine or 8 fatty material, for instance, 180 C., for a suitable period of time, such as four to twenty-four hours. Mild agitation is employed. A catalyst such as sodium oleate, sodium carbonate, caustic soda, etc., may be present in amounts of about /2% or less. It is to be noted that the fatty acids are present in ester form and not in the form of the free acid, and thus there is no tendency to form the salt to any marked extent, and if conducted at the lower range of reaction temperatures, there is a decided tendency to form the esterification products, rather than the amidification products.

In order to illustrate suitable examples of the materials, the following examples aregiven:

Intermediate amine-Example 1 Castor oil is employed. For sake of convenience, its molecular weight is considered as being 925. Commercial triethanolamine and castor 'oil in the proportion of one mole of castor oil to one mole of triethanolamine are heated at a temperature between 150 and 180 C. for about two hours. Mild agitation is employed. The reaction product so produced may be used as such, or may be converted into the acetate or other suitable form. The product is characterized-by freedom from non-esterified alkylol radicals.

35 Intermediate amine-Example 2 Polyethanolamine:

C :mo C 21140 H N-CZHAO CzH|OH is substituted for triethanolamine in, Example 1. Intermediate amine-Example 3 vious manner with the various amines above enumerated in Examples 1 and 2. In this case three moles of ethyl dihydroxy stearate is reacted with one mole of the tertiary hydroxyamine.

Intermediate amineEa:ample 4 Methyl hydroxy stearate is employed to replace ethyl dihydroxy stearate in the examples indicated under Example 3 above.

Intermediate amineEa:ample 5 Castor oil (triricinolein) is employed. For convenience, its molecular weight is considered as being 925. Commercial diethanolamine and castor oil in the proportion of two moles of castor oil to three moles of diethanolamine are heated at a temperature of 120-140 C. for about 12 hours. Mild agitation is employed. Loss of basicity is an indication of amidification. Time of reaction may be extended or temperature lowered or raised so as to insure maximum esterification. The reaction product so produced may be used as such, or may be converted into the acetate or othensuitable form. The product should be free from non-esterified alkylol radicals.

Intermediate amine-Example 6 Ethanol'amine is substituted for diethanolamine in Example 1, using three moles of ethanolamine 5 for one mole of castor oil.

amines which may be used as intermediate raw Ethyl dihydroxy stearate is reacted in the pre-,

Intermediate amineEa:ample 7 Ethyl ethanolamine is substituted for diethanolamine in Example 1, using three moles of ethyl ethanolamine for one mole of castor oil.

Intermediate amincE:cample 8 An ether amine of the following composition:

clmoclmon OZHAOCZHAOH is substituted for diethanolamine in Example 5.

Having prepared the relatively simpler intermediate amine of the kind previously described, the second step in the preparation of the new composition of matter is to produce acid esters of the kind obtainable by reaction between polybasic carboxy acids or their functional equivalents, such as the anhydrides, and hydroxylated fatty acids, esters, or the like.

The manufacture of this latter class of materials is well known, because they have been used extensively in the manufacture of demulsifiers, plasticizers, and the like. The most readily available hydroxylated fatty body is castor oil, which consists of about 85% of triricinolein. One of A OH.R.COO.CII

011.12.000.0112 then reaction products of phthalic anhydride or 'phthalic acid may be indicated in the following manner, although, for purposes of convenience, phthalic acid is not'shown in the form of the usual isomer, where, of course, the two carboxyl radicals are attached to adjacent carbon atoms:

coo.u.coo.cin'

" OH.R.COO.CH

OH.R.COO H2 CODE 0 COO.R.COO.ZH2

HO.R.COO. H

COOH

COO.R.COO.CII1

n noooOoooaCooln COO.R.COO.J3H2

COOH' COOH COO.R.COO.CH:

D OCOOJLCOQCII CO O.R.CO QH:

A large number 'of related products immediately present themselves,-for instance, esters derived by reaction with ricinoleic acid, hydroxystearicacid, dihydroxy stearic acid, and the like; or the corresponding esters derived from glycols or glycol ethers, such as ethylene glycol or diethylene glycol, which contain no free hydroxyl radicals attached to the glycol radical or residue. Similarly, one might have products derived from monohydric alcohols, for instance, ethyl ricinoleate, propyl ricinoleate, sodium ricinoleate, amylamine hydroxystearate, ammonium dihydroxystearate, etc. It is the intention to include blown oils or oxidized oils. It is not the intention to include compounds of the type in which the-hydroxyl radical is attached to a radical or residue which replaces a carboxylic hydrogen atom. For instance, it is not intended to include such materials as mono-olein, di-olein, monostearin, distearin, etc.

In the examples shown above, where the ester is polybasic, for instance, compounds of the type exemplified by C and D above, one might remove the acidity of one of the carboxylic hydrogen atoms, or two of the carboxylic hydrogen atoms, in any feasible manner, that is, by neutralization with an alkali, or by conversion into an ester involving reaction with a new kind of an alcohol, i. e., a monohydric, dihydric, trihydric, etc.

In the case of D above, two carboxylic hydrogens may be neutralized. In any event, however, the material derived by reaction between a polybasic acid or its functional equivalent and a hydroxylated fatty material of the kind described, is characterized by the presence of at least one free carboxyl radical.

Where reference is made to ricinoleic acid, hydroxystearic acid, dihydroxystearic acid, a hydroxy fatty acid, and the like, it is evident that certain simple derivatives, such as the halogenated compounds, etc., are the obvious functional equivalents; for instance, chlorinated triricinolein may be employed instead of triricinolein. Brominated ricinoleic acid might be employed instead of ricinoleic acid. In these instances the hydroxylated fatty material, notwithstanding modifications of the kind indicated, still has the same functional properties as the unmodified hydroxylated fatty material, and thus acts in the same manner as far as chemical reactions noted are concerned, and also as far as producing an effective demulsifying agent is concerned. In the hereto appended claims reference to a hydroxylated fatty material includes such obvious functional equivalents.

The polybasic acids which may be employed, including some having at least three carboxyl radicals, are phthalic, succinic', malic, fumaric, citric, maleic, adipic, tartaric, glutaric, diphenic, naphthalic, oxalic, etc.

As to the manufacture of materials of the kind desc-ribcd by reactions involving the polybasic carboxy acids or their equivalent, reference is made to the following patents, although it is not intended to infer that such patents describe these materials exclusively. However, they make such reference to the type of reaction involved that a skilled chemist would readily note the description which is particularly pertinent to the type of material just referred to: U. S.-Patent No. 1,976,602 to De Groote, Adams and Keiser, dated October 9, 1934; U. 8. Patent No. 1,977,146, to Roberts, dated October 16, .1934.

Composition of matter'E:cample 1 I substantially complete disappearance of the hydroxyl value. A suitable solvent may be present, and water formed may be distilled off continuously during the esterification process. The

solvent may remain behind in the final product,

or be removed if desired.

Composition of matter-Example 2 A similar material is prepared employing polyethanolamine in place of triethanolamine. See Example 2 described previously.

Composition of matter-Example 3 The amine obtained in the manner described in Example 3 above is employed in place of the one obtained by reaction involving castoroil and a triethanolamine, as described in Composition of matter-Example 1.

Composition of matter-Example 4 Dimaleated triricinolein is substituted for diphthalated triricinolein in Composition of mattor-Examples 1, 2 and 3, immediately above.

Composition of matter-Ewample 5 Dicitrated triricinolein is substituted for diphthalated triricinolein in Composition of matter-Examples 1, 2 and 3 immediately above.

Composition of matterE:mmple 6 Triphthalated triricinolein (see Formula D above) is substituted for diphthalated triricinolein in Composition of matter-Examples 1, 2 and 3 immediately above.

Composition of mutton-Example 7 The amine obtained by a reaction between diethanolamine, instead of triethanolamine (see Intermediate amine-Example 5 above), is substituted for the product obtained by reaction between triethanolamine and castor oil in previous Composition of matter-Examples 1 to 6, inclusive, with suitable change in molecular proportions.

It should be noted, however, that this particular product contains only two hydroxyl radicals available for esterification per atom of nitrogen, and the proper adjustment in molecular proportions should be made. Insofar that some amidifi cation may take place in following the directions in preparing the amine'from diethanolamine in Intermediate amine-Example 5 above, it is probably the safest procedure to determine the acetyl or hydroxyl value before reacting in molecular proportions, so as to leave a residual free'carboxyl radical, rather than base the mixture'of reacting compounds on theoretical stoichiometrical proportions.

Composition of matter-Eiample 8 Monophthalated hydroxystearic acid is substituted in Example 1 above, employing three moles of monophthalated hydroxystearic acid and one more of the product derived by complete esterification of triethanolamine by ricinoleic acid radicals.

C'ompositionof matter -Eazample 9 I Two moles of dihydroxystearic acid are treated with one mole of phthalic anhydride, so-as to eliminate completely any free carboxyl radicals attached to the phthalic anhydride or phthalic 'acid residue. Three moles of this product so obtained are reacted with one mole of the product derived by complete esterification of triethanolamine by ricinoleic acid radicals. (See Example 1 above).

Composition of matter-Example 10 Two molesof monophthalated hydroxystearic acid and one mole of the product derived from diethanolamine and castor oil (see Composition of matter-Example '7) are reacted in the same manner as described previously.

Composition of matter-Example 11 Two moles of dihydroxystearic acid are treated with one mole of phthalic anhydride, so as to eliminate completely any free carboxyl radicals attached to the phthalic anhydride or phthalic As previously stated, the C2H4 radical may be any one of a number of hydrocarbon radicals which are aliphatic, alicyclic, oraralkyl in nature.

It is at once manifest that similar derivatives are available from glycerols, polyglycerols, and the like, as indicated by the following reaction:

' (OHhCaHsE @EEEENH:

It is not necessary to point out that the same types of reactions will produce secondary or tertiary amines, and that the reaction is not limited to a combination with ammonia, but may take place with a combination of other primary or secondary amines, such as amylamine, diamylamine, cyclohexylamine, dicyclohexylamine, benzylamine, dibenzylamine, amyl cyclohexylamine, etc.

This means that in the type of material previously described, there is a wide variety of material, such as monoglycerylamine, diglycerylamine, monoglyceryl diethylamine, monoglyceryl dipropylamine, diglyceryl propylamine, triglycerylamine, etc., which are functional equivalents of the various amines previously described for reaction with triricinolein and the like. When such amines are employed instead of the radical CnH2nappearing in a compound, one would have in place thereof the radical -OH.C3H5; or, in case the hydroxyl radical of these OH.C3H5- radical had been removed by esterification with any available carboxyl, then the substituent which replaces the CnH2nradical might be indicated by the formula -D. C3H5-.

"All that has been said here in regard to functional acid residue. Two molesof this product so obequivalents will be perfectly obvious without further explanation to those skilled in'the art. See U. S. Patent No. 2,091,704, dated August 31, 1937, to Duncan and McAllister, and also U. S. Patent No. 2,042,621, dated June 2, 1936, to Olin.

Similarly, it is evident that where reference is made to phthalic acid, some simple derivative, such as chlorinated phthalic acid, brominated phthalic acid, methylated phthalic acid, or the like, would simply act as a functional equivalent. This applies not only ,to phthalic acid, but all the dibasic acids enumerated.

Similarly, it is evident that there is no intention to differentiate between isomeric forms. One isomeric form may serve as well as am. ther. Attention is particularly called to the ,last two examples above, which are characterized especially by the presence of a free carboxyl radical other than the carboxyl radical derived from dibasic acid. Needless to state, in the reaction between 'the ester derived by reaction between a polybasic carboxy acid material and a selected fatty material of the kind described, if there be a carboxyl radical attached to a fatty chain available for esterification, as well as a carboxyl attached to the dibasic acid, then in such event, if there is sufficient available hydroxyl radicals attached to the amine of the kind previously described, both 7 types of carboxyl radicals, i. e., (a) a carboxyl radical attached to a polyba'sic carboxy acid residue; and (b) a carboxyl radical attached to a fatty acid residue may enter into the reaction. However, my experience is that the carboxyl radi cal attached to the polybasic carboxy acid residue is generally more reactive and enters into reaction in preference to the other type of carboxyl radical, although both reactions may take place simultaneously to at least a limited degree.

I desire to emphasize that any of the products obtained in the above examples, when employed as a demulsifier in the resolution of crude oil emulsions, may be used in the form of the amine by direct contact with an emulsion without contact with water. It may be contacted with water, i. e., in the form of a solution so as to produce. in a greater or lesser degree the amine base. Furthermore, any of the products above described may be combined with a suitable acid. Acetic acid may be employed. Hydrochloric acid is particularly desirable. In some instances acids, such as oleic acid or naphthenic acid, may be employed to give a suitable salt. As previously point-- ed out, any carboxylic hydrogen atom may be replaced by a suitable metallic atom or an organic radical derived from an alcohol or from an amine.

All such ionizable hydrogen atom equivalents are considered as the functional equivalent of the ionizable' hydrogen atoms themselves, and such neutralized forms are included in the scope of the' appended claims as the equivalent of the acidic form. The expression fatty acid compound is employed to include the acid itself, as well assalts and esters thereof. It is realized that where a free carboxyl and a basic amine residue exist in the same molecule, there may be a tendency towards the formation of inner salts comparable to sulfanilic acid; but due -to the size of the molecule involved and perhaps for reasons of steric hindrance, I am not aware that such inner salts are formed.

Briefly, then, the preparation of the composition of matter herein contemplated depends on a reaction involving a polybasic carboxy acid body, or-its functional equivalent as described,

and the complex amine of the kind described, in such a manneras to involve reactions other than salt formation. amines are basic in nature, and therefore, could react with a polybasic' acid to form a salt in a manner which, for sake of convenience, will be indicated by a somewhat simpler reaction, thus:

coon

ammoocmooou coon nmmoogmcooNe Such reactions are purely salt formation. The materials of the kind herein contemplated,-regardless of their nature, are of the kind obtained by reactions other than salt formation, and also other than amidiflcation. I desire to emphasize that the expression polybasic carboxy acid, as it appearsin the claims,

refers not only to the acid itself, but to any, functional equivalent, such as the anhydride, the acyl chloride, a salt form having at least two free carboxyls, such as mono-sodium citrate, etc. It is also understood that in the heretb appended claims the nature of the final product is not limited to the form having a free carboxylic hydrogen, but that such free carboxylic hydrogen may actually be replaced by any functional equivalent of the kind previously described, for instance, a metallic atom, an ammonium radical, an amine radical, such as an amylamine radical, benzylamine radical, ethanolamine radical, diethanolamineradical, triethanolamine radical, a,hydr0- carbon radical, such as an ethyl methyl, propyl, or amyl radical, a radical derived from ethylene glycol, glycerol, or the like; a cyclohexyl radical, benzyl radical, etc. All such forms in which such ionizable hydrogen atom equivalent replaces an ionizable hydrogenatom, are obvious functional equivalents.

Attention is directed to the fact that the word.

"amidification has been applied to the reaction involvingthe replacement'of an amino hydrogen atom by an acyl radical, without conventionallimitation to a reaction involving ammonia. The

replacement of the amino hydrogen atom of a primary amine or a secondary amine by an acyl radical has been considered as being amidification, rather than the formation of a substituted amide or the formation of an imide or substituted imide. Such obvious departure from conventional-nomenclature has been for'purposes of sim-,

pliciity, and to show the similarity between certain reactions.

ricinolein, diricinolein, et'c., characterized by the M presence of a hydroxyl radical attached to the organic radical which replaces the ionizable hydrogen atom of the carboxy radical of the fatty acid.

action between an acid ester of the kind previously described and an amine of the kind previously described, is meant to refer to such products in all its various modifications previously referred to, to wit, such instances where carboxylic hydroen atoms appear as such, orhave been replaced by metallic atoms, organic radicals derived from various alcohols, amine radicals, or residues, etc.;

In other words, the complex number.

Furthermore, in the hereto appended claims, reference toithe product derived by re-.

and as to the presence of any basic amine nitrogen atom, it maybe in the amine form, or

in a salt form,:or in a base form, as, for example,

obtainable by contact with water. The functional equivalents of all these variations have been pointed out previously and were readily comprehended; and the scope of the claims, in light of such obvious equivalents, requires'no further discussion.

As to blown oils, blown fatty acids, polymerized oils, polymerized fatty acids, and other similar materials obtained by oxidation, it is understood that they may be reacted with the polybasic carboxy acids, such as phthalic acid, or phthalic anhydride to produce an acidic-ester; but it is not intended that they should be reacted with amines to produce the intermediate amine, which, in turn, is reacted with the acidic ester derived in part from a polybasic carboxy acid.

In considering the compositions of matter herein disclosed, at least to the extent that they are derived from basic diols, it'is necessary to appreciate that such substances are not resins in the sense that such term is used to indicate materials which are obtained from the same raw materials combined in different proportions and in such resins nrepresents a fairly large whole It is obvious that if one hydroxyl of triethanolamine has been esterified with a mono.- basic carboxy acid, thatthe resultant product indicated, as previously stated, by the following formula may conveniently be considered as a ols, i

OHC2H4NC2H4OH' Similarly, such a product can form a resin comparable to one obtained from the commonest dial, to wit, ethylene glycol, and would be indicated thus:

If ricinoleic acid,'be indicated thus:

OHR'COOH and the glyceride triricinolein, be indicated thus:

OH.R'GOO onn'ooo-cant OILRCOO noocOooorvcooH and diphthalated triricinolein be indicated in the following manner:

COOH

coon

like, where the two carboxyl groups are either attached to adjacent carbon atoms or carbon atoms which are relatively close together, and

to the common carbon atom chain are substantially uniform, resiniflcation takes place readily. In other words, in the product as exemplified by the diol derived by esterifying a mole of triethanolamine with a mole of a fatty acid, the product reacts readily with phthalic anhydride under proper conditions to produce a resinous material, as previously indicated. Such resinous material may be modified by introduction of a fatty acid, so as to stop further growth by reacting with the available hydroxyl. Such material as a'resin would be comparable to a modified special alkyd resin.

If, however, phthalic anhydride as such is not used in the free state, but instead, a state where one carboxyl has been united with a fatty body, such as phthalated triricinolein, phthalated ricinoleic acid, or the like, as previously described, then such materials, even though they are dibasic, do not react to produce resins, and do not build up molecules of a resinous nature in conjunction with basic diols, for various reasons, some of which are apparent and some of which are not. In the first place, steric hindrances possibly prevent random contact. In the second place, the basicity of the nitrogen atom tends to form inner salts. The space distances between carboxyl radicals become large in terms of intervening atoms. Since the alcoholic hydroxyl of ricinoleic acid is attached to the twelfth carbon atom, counting the carboxy atom as one, it means that in the radical indicated by R above there is a side chain having six more'carbon atoms, which may be an interfering group, even though. it is not depicted. Finally, the molecular reactions really involve three-dimension components, and the final product is of three dimensions. Chemical formulae, as above employed, are at the best limited to two dimensions. It is diflicult to contemplate such complex .reactionof actual three-dimensional combinations based on structural formulae of two dimensions only; However, enough has been said in this discussion to enable one to realize that the compounds herein contemplated, .particularly when .derived from basic diols, should not be confused with resinous materials.

expression diol-has been used in reference to the material derived by an esterification of one hydroxyl triethanolamine, or the like. Similarly, the expression trihydric will be conveniently used to indicate combinations that have at least three alcoholic hydroxyl. radicals, and thus would includematerials which actually have more than three; for instance, materials which have four or more hydroxyl radicals obtained, for instance, by derivatives of dihydroxy stearic acid, or from glycerylamines, or both. Obviously, a polybasic carboxy acid having more than two carboxyl radicals still acts as if it only had two carboxy radicals'in such instances where one of such radicals has been rendered inactive by esterification or salt formation, as in the instance of monosodium salt of citric acid, to which previous reference has been made.

The method of using the herein described new compound or composition of matter to resolve a petroleum emulsion of the water-in-oil type is clearly disclosed in my parent application Serial In a dibasic acid such as phthalic acid and the.

6 where the distances fromthe carboxyl radicals For convenience, in the present instance, the' No. 211,036, filed May 31, 1938, which has subsequently resulted in U. S. Patent No. 2,160,431, dated July 18, 1939, of which the present application is a continuation in part.

Having thus described my invention, what I ,claim as new and desire to secure by Letters Patent is:

1. The product resulting from an esterification reaction between (A) an amine of the formula type ouncooonnonN in which OHRCOO represents the oiw-acyl radical derived from a hydroxylated fatty acid; '1 represents a member of the class consisting of hydrocarbon radicals and non-hydroxy aeylated radicals obtained by replacing the hydrogen atom of the hydroxyl group of an alkylol radical by the acyl radical of a monobasic carboxy acid having less than 32 carbon atoms: 11. represents a small whole number which is less than 10; m represents the numeral 1, 2 or 3; m represents the numeral 0, 1 or 2, and m" represents the numeral 0, 1 or 2, with the proviso that m+m'+m"=3; and (B) an acidic ester derived by reaction between a .polybasic carboxy acid and a hydroxylated fatty acid compound; said fatty acid compound being characterized by the absence of any hydroxy substituted hydrocarbon radical as a substituent for the hydrogen atom in the carboxyl part of the hydroxy fatty acid radical; said acidic ester being characterized by the presence of at least one carboxyl radical.

2. The product resulting from an esterification reaction between (A) an amine of the formula type in which Ol-LRCOO represents the oxv-acyl radical derived from a .hydroxylated fatty acid; T represents a member of the class consisting of hydrocarbon radicals and non-hydroxy aeylated radicals obtained by replacing the hy- .drogen atom of the hydroxyl group of an alkylol radical by the acyl radical of a monobasic carboxy acid having less than 32 carbon atoms; n represents a small whole number which is less than 10; m represents the numeral 1, 2 or 3; m represents the numeral'O, 1 or 2, and m" represents the numeral 0, 1 or 2, with the proviso that m+m'+m"=3; and (B) an acidic ester derived by reaction between a dibasic carboxy acid and a hydroxylated fatty acid compound; said fatty acid compound being characterized by the absence of any hydroxy substituted hydrocarbon radical as a substituent for the hydrogen atom in the carboxy part of the hydroxy fatty acid radical; said acidic ester being characterized by the presence of at least one carboxyl radical.

3. The product resulting from an esterification reaction between (A) an amine of the formula type in which OHRCOO represents the oxy-acyl radical derived from a hydroxylated fatty acid; T represents a member of the class consisting of hydrocarbon radicals and non-hydroxy acylated radicals obtained by replacing the hydrogen atom of the hydroxyl group of an alkylol radical by the acyl radical of a monobasic carboxy acid having less than 32 carbon atoms; CnHzn being an aliphatic radical; n represents a small Whole number which is less than 10; m represents the numeral 1, 2 or 3; m represents the numeral 0, 1 or 2, and m" represents the numeral 0, 1 or 2, with the proviso that m+m'+m"=3; and (B) an acidic ester de- Y rived by reaction between a dibasic carboxy acid and a hydroxylated fatty acid compound; said fatty acid compound being characterized by the absence of any hydroxy substituted hydrocarbon radical as a substituent for the hydrogen atom in the carboxyl part of the hydroxy fatty acid radical; said acidic ester being characterized by the presence of at least one carboxyl radical.

The product resulting from an esterification reaction between (A) an amine of the formula pe (H) m t (onrooobiucmN (T) n in which OH.RCOO represents the oxy-acyl radical derived from a hydroxylated fatty acid; T represents a member of the class consisting of hydrocarbon radicals and non-hydroxy acylated radicals obtained by replacing the hydrogen atom of the hydroxyl group .of an alkylol radical by the acyl radical of a monobasic carboxy' acid having less than 32 carbon atoms; m represents the numeral 1, 2 or 3; m represents the numeral 0, 1 or 2, and m" represents the numeral 0, 1 or 2, with the proviso that m+m'+m"=3; and (B) an acidic ester derived by reaction between a dibasic carboxy acid and a hydroxylated fatty acid compound; said fatty acid compound being characterized by the absence of any hydroxy substituted hydrocarbon radical as a substituent for the hydrogen atom in the carboxylpart of the hydroxy fatty acid radical; said acidic ester being characterized by the presence of at least one carboxyl radical.

5.v The product resulting from an esterification reaction between (A) an amine of the. formula tym (OELRCOQCaHOmN in which OI-LRCOO represents the oxy-acyl radical derived from a hydroxylated fatty acid; T'represents a hydrocarbon radical; m represents the numeral 1, 2 or 3; m represents the numeral 0, 1 or 2, and 121." represents the numeral 0, 1 or 2, with the proviso that m+m'+ m"=3; and (B) an acidic ester derived by reaction between a dibasic carboxy acid and a hydroxylated fatty acid compound; said fatty acid compound being characterized by the ab--' sence of any hydroxy substituted hydrocarbon radical as a substituent for the hydrogen atom in the carboxyl part of the hydroxy fatty acid radical; said acidic ester being characterized by the presence of at least one carbonyl radical.

6. The product resulting from an esteriflcation reaction between (A) an e of the rarmula type (OHBCOOL a) mN(H) w in which OHBCOO represents the orgy-acyl radical derived from a hydrcmlated fatty acid; m

represents the numeral 1, 2 or 3; m represents the numeral 0, 1 or 2, with the proviso that m+m=3; and (B) an acidic ester derived by reaction-between a dibasic carboxy acid and a hydroxylated fatty acid compound; said fatty acid compound being characterized by the absence of any hydroxy substituted hydrocarbon radical as a substituent for the hydrogen atom in the carboxyl part of the hydroxy fatty acid radical; said acidic ester being characterized by the presence of at least one carboxyl radical.

l. The product resulting from an esteriflcation .reaction between (A) an amine of the formula ype (onncooczm) mN(H) m' in which 'OILRCOO represents the om-acyl radical derived from ricinoleic acid; m represents the numeral 1, 2 or 3; m represents the numeral tion reaction between (A) an amine of the tormula type (OHRCOQCsHa) mN (H) m' in which OH.RCOO represents-the oxy-acyl radical derived from n'cinoleic acid; m represents the numeral 1, 2 or 3, m represents the numeral 0, 1 or 2, with the proviso that m+m-'=.3; and (B) an acidic ester derived by reaction between a dibasic carboxy acid and a ricinoleic acid compound; said ric'inolei'o acid compound being characterized by the absence of any hydroxy substituted hydrocarbon radical as a substltuent for the hydrogen atom in the carbowl part or the hydroxy fatty acid radical; said acidic ester being characterized by the presence oi at least one carboxyl radical.

9. The product resulting from an 'esterification reaction between (A) an amine or the tormula type (OHRCOQCzHA) mN (H) w in which OHRCOO represents the rim-acyl radical derived from ricinoleic acid; 111. represents the numeral 1, 2 or 3; m represents the numeral 0, 1 or 2, with the proviso that m+m'=3; and (B) an acidic ester derived by reaction between a dibasic acid and triricinolein; said acidic ester being characterized by presence of at least one free carboxyl radical.

10. The product resulting from an esteriflcation reaction between (A) an amine of the formula type (OHRCOQCaHc) mN(H) m' in which OHRCOO represents the oxy-acyl radical derived from ricinoieic acid; m represents the numeral 1, 2 or 3; 122' represents the numeral Q, 1 or 2, with the proviso that m+m'="3; and (B) an acidic ester derived by reaction betweenphthalic anhydride and tricinolein; said acidic ester being characterized by the presence of at least one free carboxyl radical.

mvm DE ano. 

